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Question: If a monsterous character joins a squad can he still be singeled out in shooting?  Say a demon prince joins a 10 man marine squad.  Can he be targeted without the squad taking hits?

AFAIK, monstrous creatures can always be picked out of a squad for shooting. The Tyrant Guard are an exception to this.

Characters (ICs) that are monstrous creatures can always be targeted even if they've joined another unit (page 51 of the rulebook).

Non ICs that are part of a unit (like a Tyrant with Tyrant Guard or Tomb Spyders with Scarabs) do not follow this rule.

It even says they can be singled out under the Daemonic Stature entry.